A Ligand-Controlled Approach Enabling Gold(I)-Catalyzed Stereoinvertive Glycosylation with Primal Glycosyl ortho-Alkynylbenzoate Donors.

Abstract

A diarylurea-containing phosphine ligand-modulated stereoinvertive O-glycosylation with primal furanosyl and pyranosyl ortho-alkynylbenzoate (ABz) donors under gold(I) catalysis is disclosed. Both α- and β-configured glycosides could be obtained from the corresponding stereochemically pure β- and α-glycosyl donors with high yields and good to excellent stereoselectivities, respectively. This method accommodates a variety of glycosyl donors and alcoholic acceptors, leading to both 1,2-cis and 1,2-trans glycosidic linkages, and has been applied to the convenient preparation of a series of linear arabinan glycans. Mechanistic investigations reveal that the counteranion could bridge the diarylurea residue on the phosphine ligand with the alcoholic acceptor via hydrogen bond interactions, thereby permitting stereoinvertive displacement at the anomeric position.